title: Matrix-IR spectroscopic investigations of the thermolysis and photolysis of diazoamides.
abstract: Matrix photolysis of N,N-dialkyldiazoacetamides 1a-d at 7-10 K results in either the formation of C-H insertion products (in case of N,N-dimethyl and N,N-diethyl diazoamides) or almost exclusive Wolff rearrangement to ketenes (in the case of the cyclic diazoamides N-(diazoacetyl)azetidine and N-(diazoacetyl)pyrrolidine). This can be ascribed to higher activation barriers for the approach of the singlet carbene p orbital in 5 (or of the diazo carbon in an excited state of 1) to the stronger and "tied back" nature of the C-H bonds in the cyclic substituents. In contrast, flash vacuum thermolysis (FVT) of diazoamides 1a-d, in which reactions of excited states are excluded, gives rise to clean C-H insertion with only minor Wolff rearrangement to ketenes.
authors.affiliation: School of Chemistry and Molecular Biosciences, The University of Queensland , Brisbane, Queensland 4072, Australia.
authors.forename: Curt
authors.initials: C
authors.lastname: Wentrup
authors.forename: Hervé
authors.initials: H
authors.lastname: Bibas
authors.forename: Arvid
authors.initials: A
authors.lastname: Kuhn
authors.forename: Ullrich
authors.initials: U
authors.lastname: Mitschke
authors.forename: Mark C
authors.initials: MC
authors.lastname: McMills